Production of liquid hydrocarbons



- a phosphoric acid Patented Feb. 17, 1948 UNITED s'rzi'rss PATENT oFFice zsssm x raormc'rrou or mourn mitocanaons' Louis Schmerling, Riverside, 111., aosignor to Universal Oil Products Company, Chico: corporation of Delaware No Drawing. Application December Serial No. 032,289

alkane in the presence of a phosphoric acid catalyst.

Another object of this invention is to produce normally liquid hydrocarbons of gasoline boiling range by reacting a normally gaseous mono- 'oiefln and a monohaloalkane having at least 2 carbon atoms per molecule in the presenceoi a calcined composite of an acid of phosphorus and a carrier.

A further object of this invention is to produce normally liquid hydrocarbons by reacting ethylene and a monochloroalkane in the presence of a calcined composite of a phosphoric acid and diatomaceous earth. v

One specific embodiment of the presentinvention relates to a process for producing liquid mono-oleflnic hydrocarbons which comprises converting an olefin into a monohaloalkane and reacting said monohaloalkane and an olefin in the presence of a phosphoric acid catalyst at a temperature of from about 500 to about 750 1'.

Another embodiment of this invention relates to a process for producing mixed polymers from ethylene and a higher mono-olefin which comprises converting said higher mono-olefin into a monochloroalkane, and reacting said monochloroalkane and ethylene in the presence of a cal cined composite or a phosphoric acid and diatomaceous earth at a temperature of from about 500' to about 750 F. and at a superatmospheric pressure.

According to the process of my invention an oleiinic hydrocarbon and particularly ethylene is cross-polymerized with other oleflns by convetting the latter into monochloroalkanes and then contacting a mixture of said monochloroalkanes and the first oleii usually ethylene, with catalyst, preferably a solid phosphoric acid catalyst comprising essentially a calcined composite of an acid of phosphorus and a suitable carrier such as diatomaceous earth. This process has an advantage over the process used hitherto wherein attempts have been made to polymerize the olefin mixtures themselves, the chief advantage or my process being that it permits the utilization of ethylene, a monooleilnie hydrocarbon which does not readily polymerize with other oleflns to form cross polymers.

Acid catalysts utilizable in my process comprise particularly the acids of phosphorus including orthophosphoric, pyrophosphoric, tetraphos-- phoric'and other acids of phosphorus utilized as such or preferably supported by a suitable carrier, which is generally a siliceous material such as silica, diatomaceous earth, activated clay, etc.

Such composites of an acid of phosphorus and a carrier, after suitable mixing, are formed into particles by extrusion, drying and calcining methods or the mixed composite is calcined, crushed and screened to form particles of a desired mesh size suitable ior use as' a reactor filling material. The calcination at thevcatalyst is gen- !0 erally carried out at a temperature of from about 500 to about 1000 F. and thistreatment is tollowedby steaming at 500 to 600F. and a brief drying in air at the latter temperature.

M process is carried out by commingling a normally gaseous olefin such ethylene, propylene, etc. and a monohaloalkane in the presence of a phosphoric acid catalyst maintained at a temperature of from about 500 to about 750 F. and preferably at a superatmospheric pressure, which isusually about 200 to about 600 pounds per square inch although other pressures are utilizable which seldom exceed about 2000 pounds per square inch. This process may be etlected in either batch type treatments or it is preferably 5 carried out continuously. Continuous operation is effected by passing a mixture of a moncroleiin or a hydrocarbon fraction containing mono-oleiins, and a monohaloalkane through a heated reactor containing a granular solid phosphoric acid catalyst comprising essentially a precalcined composite of an acid of phosphorus and a carrier, such as diatomaceous earth. silica gel, etc. The resultant reaction products are then fractionally distilled or separated by other suitable means to remove unconverted mono-'oleiinic hydrocarbons and monohaloalkanes from higher boiling normally liquid products comprising essentially mono-oleflns formed in the process. Thus, when isopropyl chloride and ethylene are passed simultaneously over a calcined composite or pyrophosphoric acid and diatomaceous earth at a temperature within the above indicated limits. a normally liquid product is obtained containing heptenes, octenes, and other oleilns of higher as molecular weight. The reaction also gives ethyl chloride. the latter being suitable for recycling to the reaction to which the fresh mixture 01! ethylene and isopropyl chloride is introduced.

An alternative procedure consists in crosa-polymerizing ethylene and propylene in the presence of solid phosphoric acid catalyst and of isopropyl' chloride or hydrogen chloride, these materials be ing employed in an amount generally from about 1 to about 10% by weight of the reactants being passed over the solid catalyst.

The following example is given of results obtained by the process, although thesedata' ar not to be considered as limiting the broad scope oi the invention.

Through a steel reactor containing 20 cc. 01' 5x5 mm., pellets of a calcined composite of pyrophosphoric acid and diatomaceous earth, ethylene was passed at a rate oi. 28 liters per hour and isopropyl chloride was simultaneously; pumped through. the reactor at a rate or 36 grams per hour. A normally liquid product was obta ned at the rate or 25 gramsper hour and ethyl chloride was formed'at a rate of 25 gr ms per hour. About 1.4 molecular proportions oi ethylene were consumed per molecular proportion oi isopropyl chloride which reacted. A large amount of the ethylene which reacted was converted into ethyl chloride but the remainder copolymerized with mono-olefin which comprises reacting -a monochloroalkane and ethylene calcined composite oi a phosphoric acid and diatomaceous earth at a temperature oi from about 500 to about 750 F. and at a superatmospheric pressure.

3. A process for drocarbons which producing normally liquid hycomprises reacting a monooleilnic hydrocarbon and a monohaloalkane in the presence or a phosphoric acid catalyst at conversion conditions of temperature and pressure.

4. A process for producing normally liquid hydrocarbons which comprises reacting a monooleiinic hydrocarbon and a monochloroalkane in the presence 01' a phosphoric acid catalyst at conversion conditions of temperature and pressure.

5. A process for producing a mono-oleflnic hydrocarbon having at least 4 carbon atoms per molecule which comprises reacting a mono-olefin and a monohaloalkane having at least 2 carbon atoms per molecule in the presence of a phosphoric acid catalyst at a temperature of from about 500 to about 750 F.

6. A process for producing a mono-oleflnlc hydrocarbon which comprises reacting a normally gaseous mono-oleflnic hydrocarbon and a monohaloalkane in the presence of a calcined composite of an acid of phosphorus and a carrier at a temperature of from about 500 to about 750 F. and at a superatmospheric pressure.

propylene, forming a polymer, at least of producing liquid mono-oleflnic hydrocarbons which in the presence of a 7. A process for producing a mono-oleflnic hydrocarbon which comprises reacting a normally gaseous mono-olefinic hydrocarbon and a monochloroalkane in the presence of a calcined composite of an acid of phosphorus and diatomaceous earth at a temperature of from about 500 to about 750 F. and at a superatmospheric pressure.

8. A process for producing a mono-olefinic hydrocarbon which comprises reacting ethylene and a monochloroalkane having at least 2 carbon atoms per molecule in the presence of a calcined composite of an acid of phosphorus and diatomaceous earth at a temperature of from about 500 to about 750 F. and at a superatmospheric pressure.

LOUIS SCHMERLING.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS (Copy in Patent 

